JP2007182528A - Polymer obtained by reacting silsesquioxane derivative and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silsesquioxane-containing polymer having a high thermal stability, dissolvable with organic solvents, and excellent in film-forming property. <P>SOLUTION: This polymer is obtained by performing the hydrosilylation reaction of the silsesquioxane derivative expressed by formula (1-1) with compounds expressed by formula (a-1) to (a-5). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polymer obtained by reacting a silsesquioxane derivative. This polymer is used for electronic materials, optical materials, electro-optical materials, paints, primers, and the like.

Since a polymer using a silsesquioxane skeleton having a cage structure or a derivative thereof has a unique structure, its use in various fields has been studied. In particular, a polymer containing a silsesquioxane having a cage structure in the main chain is expected to be excellent in physical properties such as optical properties, weather resistance, and heat resistance. For example, it has been reported that hydrosilylated polymers of hydrogenated octasilsesquioxane having a cage structure with diynes and monoins having triple bonds have high thermal stability while being soluble in organic solvents. (Patent Documents 1, 2, 3 and Non-Patent Document 1). However, these polymers have a problem that even if a film is formed by a casting method, cracks are likely to occur. Further, such a polymer does not exhibit a melting point, and it is difficult to process by heat.
Patent Document 4 also discloses a polymer obtained by reacting a silsesquioxane derivative. Among them, development of a more useful polymer has been desired.
Japanese Patent Laid-Open No. 9-296043 Japanese Patent Laid-Open No. 9-296044 JP 2002-284878 A International Publication No. 2004/081085 Pamphlet Chem., Lett., 1998, 763-764

  In particular, electrical and electronic materials are required to be further improved in insulation, heat resistance, durability, moldability, and the like. However, conventional polymers containing silsesquioxane cannot satisfy these characteristics. For this purpose, a polymer with excellent heat resistance, weather resistance, electrical insulation, hardness, mechanical strength, chemical resistance, etc., having a cage-type silsesquioxane as the main chain and excellent moldability. It is desired. An object of the present invention is to provide a silsesquioxane-containing polymer that has high thermal stability, is soluble in an organic solvent, and has excellent film-forming properties.

  As a result of intensive studies to solve the above problems, the present inventors have made use of the knowledge of a polymer having a silsesquioxane derivative in the main chain disclosed in International Publication No. 2004/081085 pamphlet, In the formula (1-0) described in the literature, the compound (1-1) having two Si—H groups is reacted with a compound having a carbon-carbon triple bond in the presence of a hydrosilylation catalyst. It has been found that a new polymer can be obtained. Knowing that this polymer is soluble in an organic solvent, excellent in film-forming properties and has high thermal stability, the present invention has been completed.

式（１−１）において、Ｒは独立して炭素数１〜４０のアルキル、任意の水素がハロゲンまたは炭素数１〜２０のアルキルで置き換えられてもよいアリール、またはアリールにおける任意の水素がハロゲンまたは炭素数１〜２０のアルキルで置き換えられてもよいアリールアルキルである。ここに、炭素数１〜４０のアルキルにおいて、任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ₂−は−Ｏ−またはシクロアルキレンで置き換えられてもよく；アリールの置換基である炭素数１〜２０のアルキルにおいて、任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ₂−は−Ｏ−、シクロアルキレンまたはフェニレンで置き換えられてもよく；アリールアルキルのアルキレンにおいて、任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ₂−は−Ｏ−またはシクロアルキレンで置き換えられてもよい。
Ｒ²は独立して炭素数１〜８のアルキル、フェニル及びシクロヘキシルから選択される基である。

式（ａ−１）〜式（ａ−５）のそれぞれにおいて、Ｒ³は炭素数１〜４０のアルキレン、または任意の水素がハロゲンもしくは炭素数１〜４のアルキルで置き換えられてもよいフェニレン、ナフタレンジイル、アントラセンジイルもしくはナフタセンジイルであり；Ｒ⁴は炭素数１〜８のアルキルまたは任意の水素がハロゲンまたは炭素数１〜４のアルキルで置き換えられてもよいフェニルであり；この炭素数１〜４０のアルキレンおよび炭素数１〜８のアルキルのそれぞれにおいて、任意の−ＣＨ₂−は−Ｏ−または−ＣＯＯ−で置き換えられてもよい。
［２］式（１−１）におけるＲが独立して、炭素数１〜８のアルキル、ナフチル、任意の水素がハロゲン、メチルもしくはメトキシで置き換えられてもよいフェニル、またはベンゼン環の任意の水素がハロゲン、炭素数１〜４のアルキルもしくはメトキシで置き換えられてもよいフェニルアルキルである、［１］の重合体。
ここに、炭素数１〜８のアルキルにおいて、任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ₂−は−Ｏ−またはシクロアルキレンで置き換えられてもよく；フェニルアルキルのアルキレンにおいて、その炭素数は１〜８であり、任意の−ＣＨ₂−は−Ｏ−またはシクロアルキレンで置き換えられてよく；フェニルが複数の置換基を有するときは、それらの置換基は同一の基であってもよいし、異なる基であってもよい。
［３］式（１−１）におけるＲが、炭素数１〜８のアルキル、ナフチル、任意の水素がハロゲン、メチルまたはメトキシで置き換えられてもよいフェニル、およびベンゼン環の任意の水素がハロゲン、炭素数１〜４のアルキルまたはメトキシで置き換えられてもよいフェニルアルキルから選択される同一の基である、［１］の重合体。
ここに、炭素数１〜８のアルキルにおいて、任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ₂−は−Ｏ−またはシクロアルキレンで置き換えられてもよく；フェニルアルキルのアルキレンにおいて、その炭素数は１〜８であり、任意の−ＣＨ₂−は−Ｏ−またはシクロアルキレンで置き換えられてよく；フェニルが複数の置換基を有するときは、それらの置換基は同一の基であってもよいし、異なる基であってもよい。
［４］式（１−１）におけるＲが非置換のフェニル、シクロペンチルおよびシクロヘキシルから選択される同一の基である、［１］の重合体。
［５］式（１−１）におけるＲがフェニルであり、Ｒ²がメチルである、［１］の重合体。
［６］式（１−１）で示されるシルセスキオキサン誘導体と、下記で表される少なくとも１つの化合物とを反応させて得られる[１]〜［５］のいずれかの重合体。ここで、Ｐｈはフェニルを表す。

［７］式（１−１）で示されるシルセスキオキサン誘導体と、式（ａ−１）で示される化合物、式（ａ−２）で示される化合物、式（ａ−３）で示される化合物、式（ａ−４）で示される化合物、および式（ａ−５）で示される化合物から選ばれる少なくとも１つの化合物とを、ヒドロシリル化触媒の存在下で反応させることを特徴とする、［１］の重合体の製造方法。
［８］［１］〜［６］のいずれかの重合体を用いて得られるコーティング膜。
［９］［１］〜［６］のいずれかの重合体を用いて得られる光学素子。
［１０］［１］〜［６］のいずれかの重合体を用いて得られるディスプレイ基板。
［１１］［１］〜［６］のいずれかの重合体を用いて得られるプリント配線用基板。
［１２］［１］〜［６］のいずれかの重合体を用いて得られる耐熱塗料。
［１３］［１］〜［６］のいずれかの重合体を用いて得られる難燃・耐火塗料。
［１４］［１］〜［６］のいずれかの重合体を用いて得られる建材類コート剤。
Said subject is solved by each item shown below.
[1] A silsesquioxane derivative represented by formula (1-1), a compound represented by formula (a-1), a compound represented by formula (a-2), and a formula (a-3) A polymer obtained by reacting a compound, a compound represented by the formula (a-4), and at least one compound selected from the compounds represented by the formula (a-5).

In the formula (1-1), R is independently alkyl having 1 to 40 carbon atoms, aryl in which arbitrary hydrogen may be replaced with halogen or alkyl having 1 to 20 carbons, or arbitrary hydrogen in aryl is halogen. Or it is the arylalkyl which may be substituted by C1-C20 alkyl. Here, in the alkyl having 1 to 40 carbon atoms, any hydrogen may be replaced with fluorine, and any —CH ₂ — may be replaced with —O— or cycloalkylene; an aryl substituent. In the alkyl having 1 to 20 carbon atoms, any hydrogen may be replaced with fluorine, and any —CH ₂ — may be replaced with —O—, cycloalkylene, or phenylene; In the hydrogen atom may be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene.
R ² is a group independently selected from alkyl having 1 to 8 carbon atoms, phenyl and cyclohexyl.

In each of the formula (a-1) to the formula (a-5), R ³ is alkylene having 1 to 40 carbon atoms, or phenylene in which arbitrary hydrogen may be replaced by halogen or alkyl having 1 to 4 carbon atoms, Naphthalenediyl, anthracenediyl or naphthacenediyl; R ⁴ is alkyl having 1 to 8 carbon atoms or phenyl in which any hydrogen may be replaced by halogen or alkyl having 1 to 4 carbon atoms; In each of the alkylene and the alkyl having 1 to 8 carbon atoms, arbitrary —CH ₂ — may be replaced by —O— or —COO—.
[2] R in formula (1-1) is independently alkyl having 1 to 8 carbon atoms, naphthyl, phenyl in which arbitrary hydrogen may be replaced by halogen, methyl or methoxy, or arbitrary hydrogen in the benzene ring The polymer according to [1], wherein is halogen, phenyl having 1 to 4 carbon atoms, or phenylalkyl optionally substituted with methoxy.
Here, in the alkyl having 1 to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene; The carbon number thereof is 1 to 8, and arbitrary —CH ₂ — may be replaced by —O— or cycloalkylene; when phenyl has a plurality of substituents, the substituents are the same group. It may be a different group.
[3] R in formula (1-1) is alkyl having 1 to 8 carbon atoms, naphthyl, phenyl in which arbitrary hydrogen may be replaced with halogen, methyl or methoxy, and arbitrary hydrogen in the benzene ring is halogen, The polymer according to [1], which is the same group selected from alkyl having 1 to 4 carbon atoms or phenylalkyl optionally substituted with methoxy.
Here, in the alkyl having 1 to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene; The carbon number thereof is 1 to 8, and arbitrary —CH ₂ — may be replaced by —O— or cycloalkylene; when phenyl has a plurality of substituents, the substituents are the same group. It may be a different group.
[4] The polymer according to [1], wherein R in the formula (1-1) is the same group selected from unsubstituted phenyl, cyclopentyl, and cyclohexyl.
[5] The polymer according to [1], wherein R in the formula (1-1) is phenyl and R ² is methyl.
[6] The polymer according to any one of [1] to [5] obtained by reacting the silsesquioxane derivative represented by the formula (1-1) with at least one compound represented by the following. Here, Ph represents phenyl.

[7] A silsesquioxane derivative represented by formula (1-1), a compound represented by formula (a-1), a compound represented by formula (a-2), and a formula (a-3) A compound, a compound represented by the formula (a-4), and at least one compound selected from the compounds represented by the formula (a-5) are reacted in the presence of a hydrosilylation catalyst, 1] The method for producing the polymer.
[8] A coating film obtained using the polymer according to any one of [1] to [6].
[9] An optical element obtained using the polymer according to any one of [1] to [6].
[10] A display substrate obtained using the polymer according to any one of [1] to [6].
[11] A printed wiring board obtained using the polymer according to any one of [1] to [6].
[12] A heat resistant paint obtained by using the polymer according to any one of [1] to [6].
[13] A flame retardant / refractory paint obtained using the polymer according to any one of [1] to [6].
[14] A building materials coating agent obtained using the polymer according to any one of [1] to [6].

According to the present invention, a polymer containing a silsesquioxane skeleton in the main chain can be synthesized.
Since such a polymer has abundant rigid portions having a large molecular weight in the main chain, the thermal motion of the molecular chain can be controlled. Therefore, it can be suitably used for applications in which the movement of molecular chains is desired, for example, applications in which characteristics such as gas permeability and dimensional stability are desired. The polymer of the present invention has high solubility in an organic solvent, has excellent film forming properties and moldability, and can be used as a film, sheet and molded product. Furthermore, it has the advantage of being excellent in heat resistance, solvent resistance, adhesion to a substrate, transparency, film forming properties and the like.

The terms used in the present invention are defined as follows. Alkyl and alkylene may both be a linear group or a branched group. This is the same when any hydrogen in these groups is replaced with a halogen or a cyclic group, or when any —CH ₂ — is replaced with —O—, cycloalkylene, phenylene or the like. is there. “Arbitrary” used in the present invention indicates that not only the position but also the number is arbitrary. When a plurality of groups are replaced with another group, each group may be replaced with a different group. In addition, any of alkoxy and alkylene groups in these groups may be a linear group or a branched group. However, in the present invention, when it is described that any —CH ₂ — may be replaced by —O—, a plurality of consecutive —CH ₂ — is not replaced by —O—. Examples of halogen in the present invention are fluorine, chlorine and bromine.
In the following description, “silsesquioxane” may be represented by the symbol “PSQ”. Therefore, “silsesquioxane derivative” is expressed as “PSQ derivative”. A PSQ derivative represented by the formula (1-1) may be referred to as a compound (1-1). A compound represented by the formula (a-1) may be referred to as a compound (a-1). PSQ derivatives and compounds represented by other formulas may be simplified in the same manner.
In the chemical formula used in the present invention, Ph represents phenyl.

式（１−１）において、Ｒは独立して炭素数１〜４０のアルキル、任意の水素がハロゲンまたは炭素数１〜２０のアルキルで置き換えられてもよいアリール、またはアリールにおける任意の水素がハロゲンまたは炭素数１〜２０のアルキルで置き換えられてもよいアリールアルキルである。ここに、炭素数１〜４０のアルキルにおいて、任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ₂−は−Ｏ−またはシクロアルキレンで置き換えられてもよい。アリールの置換基である炭素数１〜２０のアルキルにおいて、任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ₂−は−Ｏ−、シクロアルキレンまたはフェニレンで置き換えられてもよい。アリールアルキルのアルキレンにおいて、任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ₂−は−Ｏ−またはシクロアルキレンで置き換えられてもよい。 Hereinafter, the present invention will be described in more detail.
The polymer of this invention is obtained by reaction which uses a compound (1-1) as one raw material.

In the formula (1-1), R is independently alkyl having 1 to 40 carbon atoms, aryl in which arbitrary hydrogen may be replaced with halogen or alkyl having 1 to 20 carbons, or arbitrary hydrogen in aryl is halogen. Or it is the arylalkyl which may be substituted by C1-C20 alkyl. Here, in the alkyl having 1 to 40 carbon atoms, arbitrary hydrogen may be replaced with fluorine, and arbitrary —CH ₂ — may be replaced with —O— or cycloalkylene. In the alkyl having 1 to 20 carbon atoms which is a substituent of aryl, arbitrary hydrogen may be replaced with fluorine, and arbitrary —CH ₂ — may be replaced with —O—, cycloalkylene or phenylene. In the arylalkyl alkylene, any hydrogen may be replaced with fluorine, and any —CH ₂ — may be replaced with —O— or cycloalkylene.

R ² is independently a group having any one of alkyl having 1 to 8 carbon atoms, phenyl, and cyclohexyl. A preferred example of R ² is alkyl having 1 to 4 carbon atoms. The most preferred example of R ² is methyl.

  In formula (1-1), it is preferable that all Rs are the same type of group, but they may be composed of two or more different types of groups. Examples of the case where 8 Rs are composed of different groups are composed of 2 or more alkyls, are composed of 2 or more aryls, are composed of 2 or more arylalkyls, When composed of at least one alkyl and at least one aryl, composed of at least one alkyl and at least one arylalkyl, composed of at least one aryl and at least one arylalkyl, etc. It is. Combinations other than these examples may be used.

When R is alkyl, the carbon number is 1-40. A preferable carbon number is 1-20. A more preferable carbon number is 1-8. Any hydrogen may be replaced with fluorine, and any —CH ₂ — may be replaced with —O— or cycloalkylene. Preferred examples of alkyl include unsubstituted alkyl having 1 to 20 carbons, alkoxyalkyl having 2 to 20 carbons, and a group in which one —CH ₂ — is substituted with cycloalkylene in alkyl having 1 to 8 carbons, Further, in each of the groups listed here, a group in which any hydrogen is replaced with fluorine, or the like. The preferable carbon number of cycloalkylene is 3-8.

  Examples of unsubstituted alkyl having 1 to 20 carbon atoms are methyl, ethyl, propyl, 1-methylethyl, butyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, hexyl, 1,1,2-trimethyl. Propyl, heptyl, octyl, 2,4,4-trimethylpentyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and the like.

  Examples of fluorinated alkyls having 1 to 20 carbon atoms are 3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-nonadecafluorohexyl, tridecafluoro- 1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, perfluoro-1H, 1H, 2H, 2H-dodecyl, perfluoro-1H, 1H, 2H, 2H- Such as tetradecyl.

  Examples of the alkoxyalkyl having 2 to 20 carbon atoms are 3-methoxypropyl, methoxyethoxyundecyl, 3-heptafluoroisopropoxypropyl and the like.

Examples of the group in which one —CH ₂ — in C 1-8 alkyl is replaced by cycloalkylene are cyclohexylmethyl, adamantaneethyl, cyclopentyl, cyclohexyl, 2-bicycloheptyl, cyclooctyl and the like.

Preferred examples in the case where R in formula (1-1) is an aryl in which arbitrary hydrogen is optionally substituted with halogen or alkyl having 1 to 20 carbon atoms are as follows: Phenyl optionally substituted with alkyl, and unsubstituted naphthyl. Here, preferred examples of halogen are fluorine, chlorine and bromine. In the alkyl having 1 to 8 carbon atoms which is a substituent of phenyl, arbitrary hydrogen may be replaced with fluorine, and arbitrary —CH ₂ — may be replaced with —O— or phenylene.

Preferred examples when R is aryl include unsubstituted phenyl, unsubstituted naphthyl, alkylphenyl, alkyloxyphenyl, phenyl with substituents including phenyl, and any hydrogen in each group listed herein. Is a group in which is replaced by halogen.
Examples of halogenated phenyl are pentafluorophenyl, 4-chlorophenyl, 4-bromophenyl and the like. Examples of alkylphenyl are 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-butylphenyl, 4-pentylphenyl, 4-heptylphenyl, 4-octylphenyl, 4-nonylphenyl, 4-decylphenyl. 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triethylphenyl, 4- (1-methylethyl) phenyl, 4- (1,1-dimethylethyl) phenyl, 4- (2-ethylhexyl) phenyl, 2,4,6-tris (1-methylethyl) phenyl and the like. Examples of alkyloxyphenyl are 4-methoxyphenyl, 4-ethoxyphenyl, 4-propoxyphenyl, 4-butoxyphenyl, 4-pentyloxyphenyl, 4-heptyloxyphenyl, 4-decyloxyphenyl, 4-octadecyloxyphenyl 4- (1-methylethoxy) phenyl, 4- (2-methylpropoxy) phenyl, 4- (1,1-dimethylethoxy) phenyl, and the like.

  Examples of phenyl having a substituent containing phenyl are 4-phenyloxyphenyl, 3-phenylmethylphenyl, biphenyl, terphenyl and the like.

  Examples of phenyl in which a part of hydrogen on the benzene ring is replaced by halogen and another hydrogen is replaced by alkyl or alkyloxy are 3-chloro-4-methylphenyl, 2,5-dichloro-4-methylphenyl 3,5-dichloro-4-methylphenyl, 2,3,5-trichloro-4-methylphenyl, 2,3,6-trichloro-4-methylphenyl, 3-bromo-4-methylphenyl, 2,5 -Dibromo-4-methylphenyl, 3,5-dibromo-4-methylphenyl, 2,3-difluoro-4-methylphenyl, 3-chloro-4-methoxyphenyl, 3-bromo-4-methoxyphenyl, 3, 5-dibromo-4-methoxyphenyl, 2,3-difluoro-4-methoxyphenyl, 2,3-difluoro-4-ethoxyphenyl, 2,3 Difluoro-4-propoxy phenyl, and the like.

Next, an example is given in which R in formula (1-1) is arylalkyl, and any hydrogen in the aryl may be replaced with halogen or alkyl having 1 to 20 carbons. In the arylalkyl alkylene, any hydrogen may be replaced with fluorine, and any —CH ₂ — may be replaced with —O— or cycloalkylene. A preferred example of arylalkyl is phenylalkyl. In this phenylalkyl, the alkylene preferably has 1 to 8 carbon atoms.
Examples of unsubstituted phenylalkyl are phenylmethyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 6-phenylhexyl, 11-phenylundecyl, 1-phenylethyl, 2-phenyl Phenylpropyl, 1-methyl-2-phenylethyl, 1-phenylpropyl, 3-phenylbutyl, 1-methyl-3-phenylpropyl, 2-phenylbutyl, 2-methyl-2-phenylpropyl, 1-phenylhexyl, etc. It is.

In phenylalkyl, any hydrogen on the benzene ring may be replaced by halogen or alkyl having 1 to 8 carbon atoms. In the alkyl having 1 to 8 carbon atoms, arbitrary hydrogen may be replaced with fluorine, and arbitrary —CH ₂ — may be replaced with —O—, cycloalkylene, or phenylene.
Examples of phenylalkyl in which any hydrogen of phenyl is replaced by fluorine are 4-fluorophenylmethyl, 2,3,4,5,6-pentafluorophenylmethyl, 2- (2,3,4,5,6 -Pentafluorophenyl) ethyl, 3- (2,3,4,5,6-pentafluorophenyl) propyl, 2- (2-fluorophenyl) propyl, 2- (4-fluorophenyl) propyl and the like.

Examples of phenylalkyl in which any hydrogen on the benzene ring is replaced by chlorine are 4-chlorophenylmethyl, 2-chlorophenylmethyl, 2,6-dichlorophenylmethyl, 2,4
-Dichlorophenylmethyl, 2,3,6-trichlorophenylmethyl, 2,4,6-trichlorophenylmethyl, 2,4,5-trichlorophenylmethyl, 2,3,4,6-tetrachlorophenylmethyl, 2,3, 4,5,6-pentachlorophenylmethyl, 2- (2-chlorophenyl) ethyl, 2- (4-chlorophenyl) ethyl, 2- (2,4,5-chlorophenyl) ethyl, 2- (2,3,6- Chlorophenyl) ethyl, 3- (3-chlorophenyl) propyl, 3- (4-chlorophenyl) propyl, 3- (2,4,5-trichlorophenyl) propyl, 3- (2,3,6-trichlorophenyl) propyl, 4- (2-chlorophenyl) butyl, 4- (3-chlorophenyl) butyl, 4- (4-chlorophenyl) butyl, 4- (2,3 6-trichlorophenyl) butyl, 4- (2,4,5-trichlorophenyl) butyl, 1- (3-chlorophenyl) ethyl, 1- (4-chlorophenyl) ethyl, 2- (4-chlorophenyl) propyl, 2- (2-chlorophenyl) propyl, 1- (4-chlorophenyl) butyl and the like.

  Examples of phenylalkyl in which any hydrogen of phenyl is replaced by bromine are 2-bromophenylmethyl, 4-bromophenylmethyl, 2,4-dibromophenylmethyl, 2,4,6-tribromophenylmethyl, 2, 3,4,5-tetrabromophenylmethyl, 2,3,4,5,6-pentabromophenylmethyl, 2- (4-bromophenyl) ethyl, 3- (4-bromophenyl) propyl, 3- (3 -Bromophenyl) propyl, 4- (4-bromophenyl) butyl, 1- (4-bromophenyl) ethyl, 2- (2-bromophenyl) propyl, 2- (4-bromophenyl) propyl and the like.

  Examples of phenylalkyl in which any hydrogen on the benzene ring is replaced with alkyl having 1 to 8 carbon atoms include 2-methylphenylmethyl, 3-methylphenylmethyl, 4-methylphenylmethyl, 4-dodecylphenylmethyl, (, 5-dimethylphenylmethyl, 2- (4-methylphenyl) ethyl, 2- (3-methylphenyl) ethyl, 2- (2,5dimethylphenyl) ethyl, 2- (4-ethylphenyl) ethyl, 2- ( 3-ethylphenyl) ethyl, 1- (4-methylphenyl) ethyl, 1- (3-methylphenyl) ethyl, 1- (2-methylphenyl) ethyl, 2- (4-methylphenyl) propyl, 2- ( 2-methylphenyl) propyl, 2- (4-ethylphenyl) propyl, 2- (2-ethylphenyl) propyl, 2- (2,3-dimethyl) Enyl) propyl, 2- (2,5-dimethylphenyl) propyl, 2- (3,5-dimethylphenyl) propyl, 2- (2,4-dimethylphenyl) propyl, 2- (3,4-dimethylphenyl) Propyl, 2- (2,5-dimethylphenyl) butyl, 4- (1-methylethyl) phenylmethyl, 2- (4- (1,1-dimethylethyl) phenyl) ethyl, 2- (4- (1- Methylethyl) phenyl) propyl, 2- (3- (1-methylethyl) phenyl) propyl, and the like.

  An example in which any hydrogen in the benzene ring is phenylalkyl substituted with alkyl having 1 to 8 carbon atoms, and hydrogen in this alkyl is substituted with fluorine is 3-trifluoromethylphenylmethyl, 2- ( 4-trifluoromethylphenyl) ethyl, 2- (4-nonafluorobutylphenyl) ethyl, 2- (4-tridecafluorohexylphenyl) ethyl, 2- (4-heptadecafluorooctylphenyl) ethyl, 1- ( 3-trifluoromethylphenyl) ethyl, 1- (4-trifluoromethylphenyl) ethyl, 1- (4-nonafluorobutylphenyl) ethyl, 1- (4-tridecafluorohexylphenyl) ethyl, 1- (4 -Heptadecafluorooctylphenyl) ethyl, 2- (4-nonafluorobutylphenyl) Propyl, 1-methyl-1- (4-nonafluorobutylphenyl) ethyl, 2- (4-tridecafluorohexylphenyl) propyl, 1-methyl-1- (4-tridecafluorohexylphenyl) ethyl, 2- (4-heptadecafluorooctylphenyl) propyl, 1-methyl-1- (4-heptadecafluorooctylphenyl) ethyl and the like.

An example in which any hydrogen of the benzene ring is phenylalkyl substituted with alkyl having 1 to 8 carbon atoms, and CH ₂ — in this alkyl is substituted with —O— is 4-methoxyphenylmethyl, 3 -Methoxyphenylmethyl, 4-ethoxyphenylmethyl, 2- (4-methoxyphenyl) ethyl, 3- (4-methoxyphenyl) propyl, 3- (2-methoxyphenyl) propyl, 3- (3,4-dimethoxyphenyl) ) Propyl, 1- (4-methoxyphenyl) ethyl, (3-methoxymethylphenyl) ethyl and the like.

An example in which any hydrogen on the benzene ring is phenylalkyl substituted with alkyl having 1 to 8 carbon atoms, and one of CH ₂ — in this alkyl is substituted with cycloalkylene, is another —CH ₂ Examples of cases where-is replaced by -O- include cyclopentylphenylmethyl, cyclopentyloxyphenylmethyl, cyclohexylphenylmethyl, cyclohexylphenylethyl, cyclohexylphenylpropyl, cyclohexyloxyphenylmethyl and the like.
An example in which any hydrogen on the benzene ring is phenylalkyl substituted with alkyl having 1 to 8 carbon atoms, and one of CH ₂ — in the alkyl is substituted with phenylene, is another example of —CH ₂ —. Examples including the case where is replaced by —O— include 2- (4-phenoxyphenyl) ethyl, 2- (4-phenoxyphenyl) propyl, 2- (2-phenoxyphenyl) propyl, and 4-biphenylylmethyl. 3-biphenylylethyl, 4-biphenylylethyl, 4-biphenylylpropyl, 2- (2-biphenylyl) propyl, 2- (4-biphenylyl) propyl, and the like.

  Examples of phenylalkyl in which at least two hydrogens on the benzene ring are replaced with different groups include 3- (2,5-dimethoxy-3,4,6-trimethylphenyl) propyl, 3-chloro-2-methylphenylmethyl, 4-chloro-2-methylphenylmethyl, 5-chloro-2-methylphenylmethyl, 6-chloro-2-methylphenylmethyl, 2-chloro-4-methylphenylmethyl, 3-chloro-4-methylphenylmethyl, 2,3-dichloro-4-methylphenylmethyl, 2,5-dichloro-4-methylphenylmethyl, 3,5-dichloro-4-methylphenylmethyl, 2,3,5-trichloro-4-methylphenylmethyl, 2,3,4,6-tetrachloro-4-methylphenylmethyl, 2,3,4,6-tetrachloro-5-methylphenylmethyl 2,3,4,5-tetrachloro-6-methylphenylmethyl, 4-chloro-3,5-dimethylphenylmethyl, 2-chloro-3,5-dimethylphenylmethyl, 2,4-dichloro-3 , 5-dimethylphenylmethyl, 2,6-dichloro-3,5-dimethylphenylmethyl, 2,4,6-trichloro-3,5-dimethylphenylmethyl, 3-bromo-2-methylphenylmethyl, 4-bromo 2-methylphenylmethyl, 5-bromo-2-methylphenylmethyl, 6-bromo-2-methylphenylmethyl, 3-bromo-4-methylphenylmethyl, 2,3-dibromo-4-methylphenylmethyl, 2 3,5-tribromo-4-methylphenylmethyl, 2,3,5,6-tetrabromo-4-methylphenylmethyl, and the like.

  The most preferred examples of phenyl in phenylalkyl are unsubstituted phenyl and phenyl having at least one of fluorine, alkyl having 1 to 4 carbon atoms and methoxy as a substituent.

Examples of phenylalkyl in which —CH ₂ — of alkylene is replaced by —O— or cycloalkylene are 3-phenoxypropyl, phenylcyclohexyl, phenoxycyclohexyl and the like.

Further preferred examples of R are unsubstituted phenyl, phenyl halide, phenyl having at least one methyl, methoxyphenyl, naphthyl, phenylmethyl, phenylethyl, phenylbutyl, 2-phenylpropyl, 1-methyl-2-phenyl Ethyl, pentafluorophenylpropyl, 4-ethylphenylethyl, 3-ethylphenylethyl, 4- (1,1-dimethylethyl) phenylethyl, 4-methoxyphenylpropyl, phenoxypropyl, cyclopentyl and cyclohexyl.
The most preferred examples of R are unsubstituted phenyl, cyclopentyl and cyclohexyl.

  Compound (1-1) used in the present invention can be produced by the method described in International Publication No. 03/024870 pamphlet.

式（ａ−１）〜式（ａ−５）のそれぞれにおいて、Ｒ³は炭素数１〜４０のアルキレン、または任意の水素がハロゲンもしくは炭素数１〜４のアルキルで置き換えられてもよいフェニレン、ナフタレンジイル、アントラセンジイルもしくはナフタセンジイルであり；Ｒ⁴は炭素数１〜８のアルキルまたは任意の水素がハロゲンまたは炭素数１〜４のアルキルで置き換えられてもよいフェニルであり；この炭素数１〜４０のアルキレンおよび炭素数１〜８のアルキルのそれぞれにおいて、任意の−ＣＨ₂−は−Ｏ−または−ＣＯＯ−で置き換えられてもよい。なお、式（ａ−１）、（ａ−４）および（ａ−５）において、Ｒ³が任意の水素がハロゲンもしくは炭素数１〜４のアルキルで置き換えられてもよいフェニレンの場合、フェニルに結合する２つの置換基の位置は、オルト、メタ、パラのいずれでもよい。
また、式（ａ−１）、（ａ−４）および（ａ−５）において、Ｒ³が任意の水素がハロゲンもしくは炭素数１〜４のアルキルで置き換えられてもよいナフタレンジイルの場合、ナフタレンに結合する２つの置換基の位置は、以下のいずれの位置でもよい。

また、式（ａ−１）、（ａ−４）および（ａ−５）において、Ｒ³が任意の水素がハロゲンもしくは炭素数１〜４のアルキルで置き換えられてもよいアントラセンジイルの場合、アントラセンに結合する２つの置換基の位置は、以下のいずれの位置でもよい。

また、式（ａ−１）、（ａ−４）および（ａ−５）において、Ｒ³が任意の水素がハロゲンもしくは炭素数１〜４のアルキルで置き換えられてもよいナフタセンジイルの場合、ナフタセンに結合する２つの置換基の位置は、以下のいずれの位置でもよい。

The compound (1-1) and at least one of the following compounds (a-1) to (a-5) having a carbon-carbon triple bond are polymerized by utilizing a hydrosilylation reaction. A polymer can be obtained.

In each of the formula (a-1) to the formula (a-5), R ³ is alkylene having 1 to 40 carbon atoms, or phenylene in which arbitrary hydrogen may be replaced by halogen or alkyl having 1 to 4 carbon atoms, Naphthalenediyl, anthracenediyl or naphthacenediyl; R ⁴ is alkyl having 1 to 8 carbon atoms or phenyl in which any hydrogen may be replaced by halogen or alkyl having 1 to 4 carbon atoms; In each of the alkylene and the alkyl having 1 to 8 carbon atoms, arbitrary —CH ₂ — may be replaced by —O— or —COO—. In the formulas (a-1), (a-4) and (a-5), when R ³ is phenylene in which arbitrary hydrogen may be replaced by halogen or alkyl having 1 to 4 carbons, phenyl The position of the two substituents to be bonded may be ortho, meta, or para.
In the formulas (a-1), (a-4) and (a-5), when R ³ is naphthalenediyl in which arbitrary hydrogen may be replaced by halogen or alkyl having 1 to 4 carbon atoms, naphthalene The position of the two substituents bonded to may be any of the following positions.

In the formulas (a-1), (a-4) and (a-5), when R ³ is anthracenediyl in which arbitrary hydrogen may be replaced by halogen or alkyl having 1 to 4 carbon atoms, anthracene The position of the two substituents bonded to may be any of the following positions.

In the formulas (a-1), (a-4) and (a-5), when R ³ is naphthacenediyl in which arbitrary hydrogen may be replaced by halogen or alkyl having 1 to 4 carbon atoms, The position of the two substituents to be bonded may be any of the following positions.

Examples of these compounds are shown below.

  In addition, the polymer of the present invention has the following formula (2-1) together with the compound (1-1) and at least one compound selected from the compound (a-1) to the compound (a-5). The weight obtained by polymerizing one or more compounds selected from the group of silicon-containing compounds represented by formula (3-1), formula (4-1), formula (5-1) and formula (6-1) It may be a coalescence.

式（２−１）において、Ｒ¹は式（１−１）におけるＲと同様に定義される基であり、その好ましい例も同様である。Ｒ¹のより好ましい例は、炭素数１〜８のアルキル、非置換のフェニル、シクロペンチル、およびシクロヘキシルであり、最も好ましい例は炭素数１〜４のアルキルおよび非置換のフェニルである。炭素数１〜４のアルキルとしてはメチルが最も好ましい。Ｘ¹¹のうち少なくとも１つは炭素−炭素三重結合を有する基であり、残りのＸ¹¹はＲ¹である。Ｘ¹¹のうちの１つまたは２つが炭素−炭素三重結合含有基である
ことが好ましい。下記の化合物は、炭素−炭素三重結合を有する化合物の一例である。

In formula (2-1), R ¹ is a group defined in the same manner as R in formula (1-1), and preferred examples thereof are also the same. More preferred examples of R ¹ are alkyl having 1 to 8 carbon atoms, unsubstituted phenyl, cyclopentyl, and cyclohexyl, and most preferred examples are alkyl having 1 to 4 carbon atoms and unsubstituted phenyl. As the alkyl having 1 to 4 carbon atoms, methyl is most preferable. At least one of X ¹¹ is a carbon - group having carbon triple bond, and the remaining X ¹¹ is R ^1. It is preferable that one or two of X ¹¹ are a carbon-carbon triple bond-containing group. The following compound is an example of a compound having a carbon-carbon triple bond.

式（３−１）において、Ｒ¹は式（１−１）におけるＲと同様に定義される基であり、その好ましい例も同様である。Ｒ¹のより好ましい例は、炭素数１〜８のアルキル、非置換のフェニル、シクロペンチル、およびシクロヘキシルであり、最も好ましい例は炭素数１〜４のアルキルおよび非置換のフェニルである。炭素数１〜４のアルキルとしてはメチルが最も好ましい。Ｘ¹¹は炭素−炭素三重結合を有する基である。そしてＬは、単結合、−Ｏ−、−ＣＨ₂−、−（ＣＨ₂）₂−、−（ＣＨ₂）₃−、−（ＣＨ₂）₄−、１，４−フェニレン、４，４’−ジフェニレン、４，４’−オキシ−１，１’−ジフェニレン、または式（ｃ）で示される基である。

The compound (3-1) is a silicon compound having a linearly bonded structure.

In formula (3-1), R ¹ is a group defined in the same manner as R in formula (1-1), and preferred examples thereof are also the same. More preferred examples of R ¹ are alkyl having 1 to 8 carbon atoms, unsubstituted phenyl, cyclopentyl, and cyclohexyl, and most preferred examples are alkyl having 1 to 4 carbon atoms and unsubstituted phenyl. As the alkyl having 1 to 4 carbon atoms, methyl is most preferable. X ¹¹ is a group having a carbon-carbon triple bond. L represents a single bond, —O—, —CH ₂ —, — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, 1,4-phenylene, 4,4 ′. -Diphenylene, 4,4'-oxy-1,1'-diphenylene, or a group represented by the formula (c).

式（３−１−１）〜式（３−１−７）において、Ｒ¹は式（３−１）におけるＲ¹と同じ意味を有し、その好ましい例も同様である。ｋは１〜４の整数であり、Ｒ³はＲ¹と同様に定義される基であり、ｍは１〜３０の整数である。そしてＸ¹¹は、炭素−炭素三重結合を有する基である。 Expression (3-1) is expanded as follows.

In formula (3-1-1) to formula (3-1-7), R ¹ has the same meaning as R ¹ in formula (3-1), and preferred examples thereof are also the same. k is an integer of 1 to 4, R ³ is a group defined similarly to R ^1, and m is an integer of 1 to 30. X ¹¹ is a group having a carbon-carbon triple bond.

式（４−１）において、Ｒ³は式（２−１）におけるＲ¹と同様に定義される基である。Ｘ¹¹の少なくとも一つは炭素−炭素三重結合を有する基であり、残りは式（１−１）におけるＲと同様に定義される基である。Ｘ¹¹の１つまたは２つが炭素−炭素三重結合を有する基であることが好ましい。そして、炭素−炭素三重結合を有する基が２つの場合はその炭素−炭素三重結合を有する基が互いに離れた位置にあることがより好ましい。Ｘ¹¹の好ましい例も式（１−１）の場合と同様である。ｅは０または１である。そして、ｎは３〜３０の整数であり、好ましいｎは４〜６である。 Compound (4-1) is a PSQ derivative having a cage structure.

In formula (4-1), R ³ is a group defined in the same manner as R ¹ in formula (2-1). At least one of X ¹¹ is a group having a carbon-carbon triple bond, and the rest are groups defined in the same manner as R in Formula (1-1). It is preferable that one or two of X ¹¹ is a group having a carbon-carbon triple bond. And when there are two groups having a carbon-carbon triple bond, it is more preferable that the groups having the carbon-carbon triple bond are in positions apart from each other. Preferred examples of X ¹¹ are the same as in the case of formula (1-1). e is 0 or 1; And n is an integer of 3-30, and preferable n is 4-6.

式（５−１）において、ＲおよびＲ¹はそれぞれ式（１−１）におけるＲと同様に定義される基である。Ｘ²¹の少なくとも１つは炭素−炭素三重結合を有する基であり、Ｘ²¹の残りはＲ¹である。Ｒの好ましい例は、式（１−１）におけるＲの場合と同じである。Ｒ¹の好ましい例は、式（２−１）におけるＲ¹の場合と同じである。 Compound (5-1) is a silicon compound having a structure in which one corner of the cage structure of octasilsesquioxane is broken.

In formula (5-1), R and R ¹ are groups defined in the same manner as R in formula (1-1). At least one of X ²¹ is a group having a carbon-carbon triple bond, and the remainder of X ²¹ is R ¹ . The preferable example of R is the same as the case of R in Formula (1-1). Preferred examples of R ¹ are the same as in R ¹ in the formula (2-1).

式（６−１）において、ＲおよびＲ¹はそれぞれ式（１−１）におけるＲと同様に定義される基である。Ｘ²¹の少なくとも１つは炭素−炭素三重結合を有する基であり、Ｘ²¹の残りはＲ¹である。Ｒの好ましい例は、式（１−１）におけるＲの場合と同じである。Ｒ¹の好ましい例は、式（２−１）におけるＲ¹の場合と同じである。 Compound (6-1) is a silicon compound having a structure in which two corners of the cage structure of octasilsesquioxane are broken.

In formula (6-1), R and R ¹ are groups defined in the same manner as R in formula (1-1). At least one of X ²¹ is a group having a carbon-carbon triple bond, and the remainder of X ²¹ is R ¹ . The preferable example of R is the same as the case of R in Formula (1-1). Preferred examples of R ¹ are the same as in R ¹ in the formula (2-1).

Compound (4-1) can be produced with reference to the method described in WO 03/004549. Compound (5-1) can be produced with reference to the method described in JP-A-2005-015738. Compound (6-1) can be produced with reference to the method described in International Publication 2004/024741 Pamphlet.
Some of the compounds used in the present invention can also be obtained from Hybrid Plastic Co. except for the compounds (1-1) and (6-1).

The molecular weight of the polymer of the present invention is appropriately set depending on the application and is not particularly limited, but the number average molecular weight is preferably 1,400 to 1,000,000, and more preferably 1,400 to 500,000.
The solvent used for hydrosilylation polymerization is not particularly limited as long as it does not inhibit the progress of the reaction. Preferred solvents are hydrocarbon solvents such as hexane and heptane, aromatic hydrocarbon solvents such as benzene, toluene and xylene, ether solvents such as diethyl ether, tetrahydrofuran (THF) and dioxane, methylene chloride, carbon tetrachloride, etc. Halogenated hydrocarbon solvents, and ester solvents such as ethyl acetate. These solvents may be used alone or in combination. Among these solvents, aromatic hydrocarbon solvents, and toluene is most preferable. A solvent is not necessarily required, but when used, a preferred ratio of the compound of the present invention to the solvent is 0.05 to 80% by weight based on the weight of the solvent. A more desirable ratio is 30 to 70% by weight. The proportion depends on the purpose.
Hydrosilylation polymerization may be carried out at room temperature. Heating may be performed to promote polymerization. It may be cooled to control exothermic or undesirable polymerization due to polymerization.
Hydrosilylation polymerization proceeds in the presence of a catalyst. Examples of preferred hydrosilylation catalysts are Karstedt catalyst, Spier catalyst, hexachloroplatinic acid and the like, which are generally well known catalysts. Since these hydrosilylation catalysts are highly reactive, the reaction can proceed sufficiently if added in a small amount. The amount used is 10 ⁻⁹ to 1 mol% in terms of the ratio of transition metal contained in the catalyst to the hydrosilyl group. A preferable addition ratio is 10 ⁻⁷ to 10 ⁻³ mol%. 10 ⁻⁹ mol% is the lower limit of the addition ratio required to allow the polymerization to proceed and be completed within an acceptable time. In consideration of keeping the manufacturing cost low, this ratio is preferably 1 mol% or less.
Next, a method for purifying the polymer will be described. This polymer is isolated and purified by efficiently removing unreacted addition polymerizable monomers. Although there are various methods, a purification method by reprecipitation operation is preferable. This purification method is performed as follows. First, in the polymerization reaction solution containing the polymer and the unreacted monomer, a solvent that does not dissolve the polymer but dissolves the unreacted monomer, a so-called precipitant is added to this solution to remove only the polymer. Precipitate. A preferred amount of the precipitating agent is 20 to 50 times based on the weight of the polymerization reaction solution.
A preferred precipitant is a solvent that is compatible with the solvent used in the polymerization, does not dissolve the polymer at all, dissolves only unreacted monomers, and has a relatively low boiling point. Examples of preferred precipitating agents are lower alcohols and aliphatic hydrocarbons. Particularly preferred precipitants are methanol and hexane. And in order to raise the removal efficiency of an unreacted monomer further, what is necessary is just to increase the repetition frequency of reprecipitation operation. By this method, only the polymer can be precipitated in a poor solvent, and the unreacted monomer and the polymer can be easily separated by a filtration operation.

  The polymer obtained by introducing a skeleton having a cage structure into the main chain has solubility, heat resistance, mechanical strength, optical permeability, gas permeability, dielectric constant, flame retardancy, adhesion, workability, etc. Is excellent. As a result, it can be used in a wide range of applications, for example, coating agents for substrates for forming metal elution prevention films, gas barrier films, antireflection films, planarization films, liquid crystal alignment films, dielectric films, etc. as electrical and electronic materials , Liquid sealing agents, semiconductor coating agents for forming interlayer insulation films, etc., microlenses, light guide plates, optical elements such as optical waveguide materials, display substrates, printed wiring boards, and heat resistant paints, flame retardant and fire resistant Examples thereof include paints and building materials coating agents. If necessary, other components such as an antioxidant, a colorant, and a filler may be blended and used in the polymer as long as the initial properties are not impaired.

When a coating film, an optical element, a display substrate, a printed wiring board, a heat resistant paint, a flame retardant / fire resistant paint, a building materials coating agent, etc. are prepared using the above-mentioned polymer, each is well known to those skilled in the art. What is necessary is just to follow a normal method. Hereinafter, the case where a coating film is formed using the polymer of this invention is demonstrated.
The polymer of the present invention is preferably used after being dissolved in a suitable solvent. The solvent used is not particularly limited as long as it is a solvent capable of dissolving the polymer. Specific examples include toluene, xylene, mesitylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, N-methyl-2-pyrrolidone, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, hexamethylphosphoric triamide, sulfolane, γ-butyrolactone, diethyl ether, THF, dioxane, dichloromethane, chloroform, 1,2-dichloroethane, alkyl lactate, 3-methyl-3-methoxybutanol, tetralin , Isophorone, ethyl acetate, ethylene glycol monoalkyl ether (such as ethylene glycol monobutyl ether), diethylene glycol monoalkyl ether (diethylene glycol monoethyl ether) Ether), ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether (propylene glycol monobutyl ether, etc.), dialkyl malonate (malon) And diethyl acid). Preferred are toluene, mesitylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, THF, ethyl acetate, and propylene glycol monomethyl ether acetate. These solvents may be used alone or in combination.

When a film is formed on a substrate, a silane-based or titanium-based coupling agent may be blended with the polymer of the present invention in order to further improve the adhesion to the substrate. Examples of silane coupling agents are aminopropyltrimethoxysilane, aminopropyltriethoxysilane, vinyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloylpropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxy (Cyclohexyl) ethyltrimethoxysilane and the like. Silicone oils such as polydimethylsiloxane and polydiphenylsiloxane may be blended.
In addition to the above coupling agent, other additives may be blended as necessary. For example, when it is desired to improve the coating property and the antistatic property, a surfactant corresponding to each purpose may be blended. Examples of the surfactant are an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, and the like, and these can be used as long as the characteristics of the membrane are not impaired.

The coating film is formed, for example, by a coating film coating solution (a solution of the polymer of the present invention) on a substrate and a subsequent baking process. As the substrate, a glass substrate, a plastic substrate, a film substrate, or the like can be used. As a coating method, a spinner method, a spray method, a dipping method and the like are generally known. These methods are similarly applicable in the present invention. Further, as a method for baking a coating film coating solution, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known. These methods are equally applicable in the present invention. Moreover, it is preferable to perform a heat processing process under the temperature of about 80-300 degreeC generally.

  The present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. In the chemical formulas in the examples, Me is methyl and Ph is phenyl.

The test method in an Example is demonstrated below.
(1) Each spectrum of ¹ H-NMR, ¹³ C-NMR, and ²⁹ Si-NMR was measured using a JNM-AL 300 spectrometer manufactured by JOEL.
(2) The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured by GPC. In GPC, one column SHODEX GPC-101 manufactured by Showa Denko KK and two SHODEX LF-804s were connected and used, THF was used as a developing solvent, and polystyrene having a known molecular weight was used as a standard substance.
(3) MALDI-TOF MS was performed using an AXIMA-CFA mass spectrometer manufactured by Shimadzu Corporation.
(4) Differential scanning calorimetry (DSC) was performed using a Seiko DSC6200 while heating at 10 ° C./min in a nitrogen atmosphere.
(5) Thermogravimetric analysis (TGA) was performed using a Seiko DSC6200 while heating at 10 ° C./min in a nitrogen atmosphere.

Example 1
Under an argon atmosphere, Compound (1) (1.154 g), diphenylacetylene (0.356 g), toluene (2 mL), and karsted catalyst (20 μl) were added to a 20 mL Schlenk flask, and the mixture was stirred at 100 ° C. for 24 hours. After completion of the reaction, toluene was removed under reduced pressure, and the compound obtained by fractionation by GPC was evaluated using ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-NMR and MALDI-TOF MS. This was confirmed to be the compound (2). The yield at this time was 1.111 g (74% yield).

なお、式（４）中、下記

のように記載されている部分は、重合体が下記の（Ａ）の結合状態および（Ｂ）の結合状態の混合物として得られることを表している。後述の式（６）においても同様である。
Example 2
A polymer was synthesized by reacting in the same manner as in Example 1 except that 0.278 g of the compound represented by the following formula (3) was used instead of diphenylacetylene. The polymer was recovered by reprecipitation using methanol as a poor solvent. When the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the obtained polymer were determined by GPC, Mn = 29,100 and Mw / Mn = 4.1. The thermal decomposition starting temperature determined from TGA was 518 ° C., and the glass transition temperature determined from DSC was 153 ° C. Moreover, the polymer obtained using < ¹ > H-NMR, < ¹³ > C-NMR, < ²⁹ > Si-NMR was evaluated, and it confirmed that it was a structure shown by Formula (4).

In formula (4), the following

The part described as follows indicates that the polymer is obtained as a mixture of the following bonded state (A) and bonded state (B). The same applies to equation (6) described later.

化合物（１）を１．３８４ｇ、化合物（３）を０．３３４ｇ用いた以外は実施例１と同様の方法で反応を行い、重合体を合成した。重合体はメタノールを貧溶媒として再沈殿法により回収した。得られた重合体の数平均分子量（Ｍｎ）および分子量分布（Ｍｗ／Ｍｎ）をＧＰＣで求めたところ、Ｍｎ＝１４，６００、Ｍｗ／Ｍｎ＝２．９であった。ＴＧＡより求めた熱分解開始温度は４８９℃、ＤＳＣより求めたガラス転移温度は１５６℃であった。 Example 3

A polymer was synthesized by reacting in the same manner as in Example 1 except that 1.384 g of compound (1) and 0.334 g of compound (3) were used. The polymer was recovered by reprecipitation using methanol as a poor solvent. When the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the obtained polymer were determined by GPC, Mn = 14,600 and Mw / Mn = 2.9. The thermal decomposition starting temperature determined from TGA was 489 ° C., and the glass transition temperature determined from DSC was 156 ° C.

Example 4
A polymer was synthesized by reacting in the same manner as in Example 1 except that 0.378 g of the compound represented by the following formula (5) was used instead of diphenylacetylene. The polymer was recovered by reprecipitation using methanol as a poor solvent. When the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the obtained polymer were determined by GPC, Mn = 11,900 and Mw / Mn = 4.9. The thermal decomposition starting temperature determined from TGA was 301 ° C. ^The polymer obtained by using ¹ H-NMR, ¹³ C-NMR, and ²⁹ Si-NMR was evaluated and confirmed to have a structure represented by the formula (6).

Example 5
A polymer was synthesized by reacting in the same manner as in Example 1 except that 0.278 g of the compound represented by the following formula (7) was used instead of diphenylacetylene. The polymer was recovered by reprecipitation using methanol as a poor solvent. When the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the obtained polymer were determined by GPC, Mn = 26,500 and Mw / Mn = 5.4. The thermal decomposition starting temperature determined from TGA was 510 ° C., and the glass transition temperature determined from DSC was 137 ° C.

The compound of formula (7), 1,3-Bis (phenylethynyl) benzene, was synthesized as follows.
After adding iodobenzene 4.12 g (20.2 mmol), CuI 0.04 g (0.2 mmol), (Ph ₃ P) ₂ PdCl ₂ 0.14 g (0.2 mmol), and diisopropylamine 90 ml to a 100 ml three-necked flask, 1,3-diethynyl 10 ml of a diisopropylamine solution containing 1.26 g (10.1 mmol) of -benzene was added dropwise. The reaction solution was stirred at room temperature for 24 hours, and then diisopropylamine as a solvent was removed under reduced pressure. The residue was dissolved in toluene, washed with aqueous NaCl solution, and dried over MgSO ₄ . The solvent was removed using an evaporator, followed by purification by flash column chromatography using alumina. Finally, recrystallization with MeOH was performed to obtain 1.39 g of white crystals. Yield: 50% ¹ H NMR (300 MHz, CDCl ₃ ): δ (ppm) 7.34 (br, 7H), 7, .50 (br, 6H), 7.70 (br, 1H). ¹³ C NMR (75 MHz , CDCl ₃ ): δ (ppm) 88.5, 89.9, 123.0, 123.6, 128.3, 128.4, 131.3, 131.6, 134.6.

Example 6
A polymer was synthesized by reacting in the same manner as in Example 1 except that 0.354 g of the compound represented by the following formula (8) was used instead of diphenylacetylene. The polymer was recovered by reprecipitation using methanol as a poor solvent. When the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the obtained polymer were determined by GPC, Mn = 25,700 and Mw / Mn = 5.1. The thermal decomposition starting temperature determined from TGA was 474 ° C., and the glass transition temperature determined from DSC was 184 ° C.

The compound of formula (8), 4,4′-Bis (phenylethynyl) biphenyl, was synthesized as follows.
After adding 4,4'-diiodobiphenyl 2.03 g (5 mmol), CuI 0.02 g (0.1 mmol), (Ph ₃ P) ₂ PdCl ₂ 0.07 g (0.1 mmol), and diisopropylamine 35 ml to a 100 ml three-necked flask, ethynylbenzene 5 ml of diisopropylamine solution containing 1.03 g (10.1 mmol) was added dropwise. Reaction solution at room temperature
After stirring for h, the solvent diisopropylamine was removed under reduced pressure. The residue was dissolved in toluene, washed with aqueous NaCl solution, and dried over MgSO ₄ . The solvent was removed using an evaporator, followed by purification by flash column chromatography using alumina. Finally, recrystallization with MeOH was performed to obtain 1.06 g of white crystals. Yield: 60% ¹ H NMR (300 MHz, CDCl ₃ ): δ (ppm) 7.35 (br, 6H), 7.53 (br, 4H), 7.60 (br, 8H). ¹³ C NMR (75 MHz, CDCl ₃ ): δ (ppm) 89.2, 90.3, 122.6, 123.1, 126.9, 128.3, 128.4, 131.6, 132.1, 140.0.

Claims (14)

Silsesquioxane derivative represented by formula (1-1), compound represented by formula (a-1), compound represented by formula (a-2), compound represented by formula (a-3), formula A polymer obtained by reacting a compound represented by (a-4) and at least one compound selected from compounds represented by formula (a-5).

In the formula (1-1), R is independently alkyl having 1 to 40 carbon atoms, aryl in which arbitrary hydrogen may be replaced with halogen or alkyl having 1 to 20 carbons, or arbitrary hydrogen in aryl is halogen. Or it is the arylalkyl which may be substituted by C1-C20 alkyl. Here, in the alkyl having 1 to 40 carbon atoms, any hydrogen may be replaced with fluorine, and any —CH ₂ — may be replaced with —O— or cycloalkylene; an aryl substituent. In the alkyl having 1 to 20 carbon atoms, any hydrogen may be replaced with fluorine, and any —CH ₂ — may be replaced with —O—, cycloalkylene, or phenylene; In the hydrogen atom may be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene.
R ² is a group independently selected from alkyl having 1 to 8 carbon atoms, phenyl and cyclohexyl.

In each of the formula (a-1) to the formula (a-5), R ³ is alkylene having 1 to 40 carbon atoms, or phenylene in which arbitrary hydrogen may be replaced by halogen or alkyl having 1 to 4 carbon atoms, Naphthalenediyl, anthracenediyl or naphthacenediyl; R ⁴ is alkyl having 1 to 8 carbon atoms or phenyl in which any hydrogen may be replaced by halogen or alkyl having 1 to 4 carbon atoms; In each of the alkylene and the alkyl having 1 to 8 carbon atoms, arbitrary —CH ₂ — may be replaced by —O— or —COO—. R in formula (1-1) is independently alkyl having 1 to 8 carbon atoms, naphthyl, phenyl in which arbitrary hydrogen may be replaced by halogen, methyl or methoxy, or any hydrogen in the benzene ring is halogen, The polymer according to claim 1, which is phenylalkyl which may be substituted with alkyl having 1 to 4 carbon atoms or methoxy.
Here, in the alkyl having 1 to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene; The carbon number thereof is 1 to 8, and arbitrary —CH ₂ — may be replaced by —O— or cycloalkylene; when phenyl has a plurality of substituents, the substituents are the same group. It may be a different group. R in formula (1-1) is alkyl having 1 to 8 carbon atoms, naphthyl, phenyl in which arbitrary hydrogen may be replaced by halogen, methyl or methoxy, and arbitrary hydrogen in the benzene ring is halogen, having 1 carbon atom The polymer of claim 1, which is the same group selected from phenylalkyl optionally substituted with ~ 4 alkyl or methoxy.
Here, in the alkyl having 1 to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene; The carbon number thereof is 1 to 8, and arbitrary —CH ₂ — may be replaced by —O— or cycloalkylene; when phenyl has a plurality of substituents, the substituents are the same group. It may be a different group. The polymer according to claim 1, wherein R in the formula (1-1) is the same group selected from unsubstituted phenyl, cyclopentyl, and cyclohexyl. Wherein R is phenyl in the formula (1-1), R ² is methyl, the polymer of claim 1. The polymer as described in any one of Claims 1-5 obtained by making the silsesquioxane derivative shown by Formula (1-1), and the at least 1 compound represented below react. Here, Ph represents phenyl.

Silsesquioxane derivative represented by formula (1-1), compound represented by formula (a-1), compound represented by formula (a-2), compound represented by formula (a-3), formula The compound represented by (a-4) and at least one compound selected from the compounds represented by formula (a-5) are reacted in the presence of a hydrosilylation catalyst. The manufacturing method of the polymer of description.

In the formula (1-1), R is independently alkyl having 1 to 40 carbon atoms, aryl in which arbitrary hydrogen may be replaced with halogen or alkyl having 1 to 20 carbons, or arbitrary hydrogen in aryl is halogen. Or it is the arylalkyl which may be substituted by C1-C20 alkyl. Here, in the alkyl having 1 to 40 carbon atoms, any hydrogen may be replaced with fluorine, and any —CH ₂ — may be replaced with —O— or cycloalkylene; an aryl substituent. In the alkyl having 1 to 20 carbon atoms, any hydrogen may be replaced with fluorine, and any —CH ₂ — may be replaced with —O—, cycloalkylene, or phenylene; In the hydrogen atom may be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene. R ² is a group independently selected from alkyl having 1 to 8 carbon atoms, phenyl and cyclohexyl.

In each of the formulas (a-1) to (a-5), R ³ represents alkylene having 1 to 40 carbon atoms or phenylene or naphthalene in which arbitrary hydrogen may be replaced by halogen or alkyl having 1 to 4 carbon atoms Diyl, anthracenediyl or naphthacenediyl; R ⁴ is alkyl having 1 to 8 carbon atoms or phenyl in which any hydrogen may be replaced by halogen or alkyl having 1 to 4 carbon atoms; In each of alkylene and alkyl having 1 to 8 carbons, arbitrary —CH ₂ — may be replaced by —O— or —COO—. The coating film obtained using the polymer of any one of Claims 1-6. The optical element obtained using the polymer of any one of Claims 1-6. A display substrate obtained by using the polymer according to claim 1. The printed wiring board obtained using the polymer of any one of Claims 1-6. The heat-resistant coating material obtained using the polymer of any one of Claims 1-6. The flame-retardant and fire-resistant coating material obtained using the polymer of any one of Claims 1-6. A building materials coating agent obtained by using the polymer according to any one of claims 1 to 6.